New indigoid dyestuffs of the anthraquinone series



, (Ill Patented Sept. 20, 1932 rarer creme A HEINRICH BITTER AND WALTERBRUNNER,. OF FBANKFORT-ON-THE-MAIN-FECHEN- I-IEIM, GERMANY, ASSIGNORS TOGENERAL ANILINE WORKS, INC., OF NEW YORK,

N. Y., A CORPORATION OF DELAWARE i NEW INDIGOID DYESTU'FFS OF THEANTHRAQUINONE SERIES No Drawing. Application filed April 14, 1931,Serial No. 530,134, and in Germany April 23, 1930.

Our present invention relates to new indigoid dyestuffs of theanthraquinone series which are derived from anthr'aquinone-LQ- (whereinR means a radical of the benzene,

naphthalene or anthraquinone series and X means S or NH).

The dyestuffs may be prepared by the fol lowing methods:

The symmetrical thioindigo is obtained by treating anthraquinone 1.2oxythiophene with an oxidizing agent. Asymmetrical dyestuffs areproduced by condensing this anthraquinone-1.2-oxythiophene with one ofthe customary components of'indigoid dyestuffs, for instanceortho-diketones, such as acenaphthenequinone, isatines or theirchlorides, oxythionaphethenes or their anils or by condensing an anil ofanthraquinone-12-oxy thiophene with compounds containing reactivemethylene group oxythiophene and correspond to the general formula: 1 rV In order to further'illustrate our invention the following examplesare given, the parts being by weight and all temperatures in centi gradederees; but we wish it to be understood that our invention is notlimited to the examples given nor to the reacting conditions mentionedtherein.

Example 1 10 parts of anthraquinone-l.2-oxythiophene are dissolved inabout 500 parts of a 2% caustic soda lye and to this solution a solutionof separates as a reddish-brown precipitate. It

is filtered, washed and dried. It dyes cotton from an orange-brown vatbrownish shades and dissovles in concentrated sulfuric acid to a puregreen solution. I

Instead of potassium ferricyanide, hydrogen peroxide, persulfate orother similarly acting oxidizing agents maybe used.

Example 2 80 parts of 5.7-dibromo-isatine are converted into thechloride by treating 1t at 100105 with 22 parts of phosphoruspentachloride in 500 parts of mono-chlorobenzene. This solution iscondensed at380-90" with a mixture of 28 parts of'anthraquinone-1.2-oxythiophene and 2000 parts of mono chlorobenzene. The new dyestuif1mme d1- ately precipitates as dark blue crystals WhlCh are filtered anddried. It corresponds to the following formula: t

S-G:ONH

ll 1 l ml. $0.... I

It dissolves in concentrated sulfuric acid with a green tlnt and dyescotton from an orange vat grey shades.

Emample 3 21 parts of 9-chloro-a-naphthisatine are converted into thechloride by treating it at 100105 with 22 parts of phosphoruspentachloride in 500 parts of mono-chlorobenzene. This solution iscondensed at 90l00- with a mixture of 28 parts ofanthraquinone-L2-oxythiophene and 2000 parts of mono-chlorobenze'ne. Thenew dyestuif immediately precipitat-es in the form of dark violetcrystals which are filtered and dried. It corresponds to the followingformula green tintand dyeing cotton from a yellowlsh red .vat greyishgreen shades.

u Example 4 103 parts ofanthraquinone-l.2-oxythiophene-2-(paradimethylamino)-anil and parts 0f6-ethoxy-oxythionaphthene are heated in-2000 parts of glacial aceticacid to 100105 for 5 hours. By filtering and drying a brown powder isobtained which dyes cotton from a yellowish red vat yellowish brownshades and corresponds to the formula:

" o 's-o=o -s Altai By replacing 6-ethoXy-oXythionaphthene by6-chloro-oxythionaphthene a reddish brown dye1ngproduct is obtained.

Ewample 5 80 parts of, 2.1-naphthoXythiophene-2- a (para-dimethylamino)-ani1 and parts of anthraquinone-l.2-oxythiophene are heated inabout 2000 parts of glacial acetic acid to 100105 for 67 hours. Byfiltering and drying a darlr brown powder is obtained which dissolves inconcentrated sulfuric acid with a bluish green tint and dyes cotton froma yellowish redat brown shades. It corresponds to the following formula:

* dd t Y U- By replacing the anil of 2.1-naphthoxythiophene by that of2.3-naphthoxythiophene a black powder is obtained which dissolves inconcentrated sulfuric. acid withan olive-green tint-and dyes? cottonfrom a red vat greenish grey shades. p 1

Example 6" 6 parts of 9-chloro-a-naphthisatine and 0 parts ofanthraquinone-1.2-oXythiophene e well stirred in 2000 parts of glacialaceic acid then mixed with 5 parts of concentrated hydrochloric acid and.boiled for about 5 hours. By filtering and drying a dark powder isobtained soluble inconcentrated sulfuric acid witha brown tint anddyeing cotton from a yellowish brown vat yellowish olive shades. Thisproduct contains probably the dyes'tuff of the following formula oo-aynm We claim:

1. As new compounds the indigoid dyestuffs of the anthraquinone seriescorresponding to the general formula ging 1 (wherein R means a radicalof thelbenzene,- naphthalene or anthraquinoneiseriesand X. means S orNH), which dyestuffs dye the vegetable ,fiber brown grey to olive greyshades of a good fastness "and levelling power.

2.- As new compounds the indigoid dyestuffs of the anthranquinone seriescorre-' sponding to the general formula:

"t ol '(whereinR" means a naphthalene nucleus which may be halogenatedand X means so or NH), which dyestuffs dye the vegetable fiber brown,grey to olive grey shades of a good fastness and levelling power. I

3. As a new compound the indigoid dyestuff of the probable formula:

'\ to Cl which dyestufi' forms dark violet crystals dissolving inconcentrated sulfuric acid with an olive green tint, dyeing cotton froman orange brown vat full olive-green shades of a good fastness.

4. As a new compound the indigoid dyestuff of the probable formula:

owlool' which dyestufi forms a dark brown powder dissolving inconcentrated sulfuric acid with a bluish green tint, dyeing cotton froma yellowish red vat brown shades of a good fastness.

In testimony whereof, we affix our signatures.

HEINRICH BITTER. WALTER BRUNNER.

